Electron transfer and localization in endohedral metallofullerenes: Ab initio density functional theory calculations

Endohedral metallofullerenes constitute an appealing class of nanoscale building blocks for fabrication of a wide range of materials. One open question of fundamental importance is the precise nature of charge redistribution within the carbon cages (C_n) upon metal encapsulation. Using ab initio density functional theory, we systematically study the electronic structure of metallofullerenes, focusing on the spatial charge redistribution. For large metallofullerenes (n>32), the valence electrons of the metal atoms are all transferred to the fullerene states. Surprisingly, the transferred charge is found to be highly localized inside the cage near the metal cations rather than uniformly distributed on the surfaces of the carbon cage as traditionally believed. This counterintuitive charge localization picture is attributed to the strong metal-cage interactions within the systems. These findings may prove to be instrumental in the design of fullerene-based functional nanomaterials.